Optical and EPR study of BaY2F8 single crystals doped with Yb

Optical and electron paramagnetic resonance study have been carried out on BaY₂F₈ single crystals doped with Yb ions at 0.5 and 10 mol%. The crystals have been obtained using the Czochralski method modified for fluoride crystal growth. Optical transmission measurements in the range of 190-3200 nm and photoluminescence measurements were carried out at room temperature. Absorption spectra of BaY₂F₈ single crystals doped with Yb due to the ²F_7/2→²F_5/2 transitions have been observed in the 930-980 nm range. To analyze the possible presence of Yb²⁺ ions in the investigated crystals, irradiation with γ-quanta with a dose of 10⁵ Gy have been performed. The observed photoluminescence bands show usual emission in IR and other one in VIS, being an effect of cooperative emission of Yb³⁺ ions and energy up-conversion transitions of photons from IR to UV-vis(visible) due to hoping process between energy levels of paired Yb³⁺ and Er³⁺, where Er³⁺ ions are unintentional dopants. The EPR spectra of BaY₂F₈:Yb 10 mol% consist of many overlapping lines. They have been analyzed in terms of spin monomers, pairs, and clusters. The angular dependence of the resonance lines positions have been studied also to find the location of coupled ytterbium ions in the crystal structure.     

Electron spin resonance study of a CuIr2S4 single crystal

A spinel sulphide CuIr₂S₄ single crystal, which exhibits an orbitally induced Peierls phase transition at ～230?K, is investigated by electron spin resonance (ESR) spectroscopy. The phase transition is clearly manifested on the ESR spectra. It is suggested that the ESR signals are produced by a few non-dimerized Ir⁴⁺ ions. Moreover, an extra ESR spectrum appears at low temperature in addition to the paramagnetic ESR signals of Ir⁴⁺ ions, which is suggested to be caused by the Jahn–Teller effect of the non-dimerized Ir⁴⁺ ions. From the ESR results, it is found that the Jahn–Teller splitting energy ΔE _JT is much smaller than the spin-dimerization gap.     

Magnetic structures and crystal field in the heavy electron materials YbAgGe and YbPtIn

We have examined the magnetic properties of the heavy electron compounds YbAgGe and YbPtIn by ¹⁷⁰Yb M?ssbauer spectroscopy down to 0.1 K, and the crystal field properties of YbAgGe by Perturbed Angular Correlations (PAC) measurements up to 900 K. In YbAgGe, we show that each of the two magnetically ordered phases below 0.8 K involves a specific incommensurate modulation of the Yb moment. An analysis of existing low temperature specific heat data suggests the persistence of fluctuations of the correlated Yb spins down to 0.1 K. The PAC data allow to discriminate among proposed Yb³⁺ crystal field level schemes. In YbPtIn, we show that the low temperature magnetic order phase has an antiferro-para structure, where zero moment Yb ions coexist with large moment ones, and that a 90° moment reorientation occurs at 1.4 K.     

EPR of Yb<Superscript>3+</Superscript> ions in a monoclinic KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> single crystal

The electron paramagnetic resonance (EPR) of Yb³⁺ ions in a KY(WO₄)₂ single crystal was investigated at T=4.2 K and fixed frequency of 9.38 GHz. The resonance absorption observed on the lowest Kramers doublet represents the complex superposition of three spectra, corresponding to the ytterbium isotopes with different nuclear moments. The EPR spectrum is characterized by a strong anisotropy of the g-factors. The temperature dependence of the g-factors is shown to be caused by the strong spin-orbital and orbital-lattice coupling. The resonance lines broaden with increasing temperature due to the short spin-lattice relaxation times.     

A comparison of selected organic tracers for quantitative scalar imaging in the gas phase via laser-induced fluorescence

Single crystal of La₃Ga_5.5Ta_0.5O₁₄ (LGT) containing intentionally 0.5 % of Ho³⁺ and 1 % of Yb³⁺ was grown by the Czochralski method. Examination of chemical composition of the grown crystal revealed that luminescent holmium and ytterbium ions are preferably retained in the melt and their actual concentrations are 0.12 and 0.24 %, respectively. Spectroscopic investigation performed encompassed IR host absorption spectra and Raman spectra at room temperature, optical absorption and luminescence spectra of Ho³⁺ and Yb³⁺ at room temperature and at 5 K, and luminescence decay curves at room temperature. It was found that all spectral bands recorded show important inhomogeneous line broadening. This feature was attributed to structural disorder inherent to the crystal lattice in which pentavalent Ta⁵⁺ ions occupy octahedral Ga(1) sites together with trivalent Ga³⁺ ions. Despite small concentrations of luminescent ions, the occurrence of nonradiative interaction that feeds the ⁵I₆ and ⁵I₇ levels of Ho³⁺ ions by transfer of an excitation from the ²F_5/2 level of Yb³⁺ ions was evidenced. Based on examination of spectroscopic parameters evaluated, it was concluded that LGT:Ho, Yb may be considered as a potential intermediate-gain laser active material able to emit infrared radiation from the ⁵I₇ → ⁵I₈ transition of Ho³⁺ around 2 micrometres upon laser-diode pumping into Yb³⁺ absorption band.     

Spectral properties and energy transfer of Yb,Er:GdVO4 crystal

GdVO₄ single crystal co-doped with Yb³⁺ and Er³⁺ was grown by the Czochralski method. The X-ray powder diffraction pattern of Yb,Er:GdVO₄ crystal confirms that the as-grown crystal is isostructural with pure GdVO₄ crystal. Its polarized absorption spectra and non-polarized fluorescence spectra were measured at room temperature. The absorption band at 984 nm for π-polarization has an FWHM of about 36 nm, which is favorable for InGaAs LD laser pumping. The spectrum properties of Er³⁺ in Yb,Er:GdVO₄ crystal were investigated based on Judd–Ofelt theory. There is strong energy transfer from Yb³⁺ to Er³⁺ in this crystal. When excited with 980 nm radiation, this crystal emitted strong fluorescence at about 1529 nm and 552.5 nm. The total energy transfer rate and efficiency from Yb³⁺ to Er³⁺ is 3.33 ms^-1 and 67%, respectively. The energy transfer between Er³⁺ and Yb³⁺ ions is a multistep transfer process, and was investigated based on a random-walk model. The investigation result shows that there is strong cooperative-sensitization effect from Yb³⁺ to Er³⁺, which is the main upconversion energy-transfer process in this crystal. PACS 42.70.Hj; 81.10.Fq; 42.55.Rz     

Crystal growth, optical properties, and laser operation of Yb3+-doped NYW single crystal

Laser crystal Yb³⁺-doped NaY(WO₄)₂ (Yb:NYW) with excellent quality has been grown by Czochralski technique. The rocking curves from (400) plane of as-grown Yb:NYW crystal was measured and the full-width value at half-maximum was 19.92″. The effective segregation coefficients were measured by the X-ray fluorescence method. The polarized absorption spectra and the fluorescence spectra of Yb:NYW crystal were measured at room temperature. The fluorescence decay lifetime of Yb³⁺ ion in NYW crystal has been investigated. The spectroscopic parameters of Yb:NYW crystal are calculated and compared with those of Yb:YAG crystal. A continuous wave output power of 3.06 W at 1031 nm was obtained with a slope efficiency of 42% by use of diode pumping.     

Temperature dependence of the EPR lines in weakly doped LiNbO3:Yb—possible evidence of Yb ion pairs formation

The electron paramagnetic resonance (EPR) studies of LiNbO₃ single crystal doped with 1 wt% of Yb³⁺ are reported. To put the EPR results in perspective, a brief discussion of optical absorption spectroscopy investigations of LiNbO₃:Yb³⁺ is provided. The temperature behavior of the EPR lines intensity and linewidth for LiNbO₃:Yb³⁺ reveals antiferromagnetic coupling between Yb³⁺ ions. The deconvolution of the EPR lines indicates that EPR signals arise from both the isolated Yb³⁺ ions as well as the Yb³⁺-Yb³⁺ ion pairs; the latter signals dominate. Based on this indication, EPR spectra are interpreted using a spin Hamiltonian for the Yb³⁺ dissimilar ion pairs. The negative sign of the isotropic parameter J confirms the existence of the antiferromagnetic interactions within Yb³⁺-Yb³⁺ pairs. The value of J obtained based on the proposed pair model, assuming the dipole-dipole interactions, is used to identify the positions of the Yb³⁺-Yb³⁺ pairs in the unit cell. Our results suggest the ^evenYb³⁺-^evenYb³⁺ pairs are located at the neighboring Li⁺ and Nb⁵⁺ positions, whereas the pair axis is not parallel to the optical c-axis. Some alternative explanations of the observed EPR spectra are also considered.     

Analysis of the structure of tetragonal oxygen centers associated with Yb<Superscript>3+</Superscript> ions in the KMgF<Subscript>3</Subscript> crystal

The parameters of the crystal field of the tetragonal oxygen center associated with a Yb³⁺ ion in the KMgF₃ crystal found previously in a study of optical and ESR spectra are applied to analyze lattice distortions in the vicinity of the impurity ion and the O^2? ion compensating for the excess positive charge. Within the superposition model, it was ascertained that the Yb³⁺ ion and the neighboring ions of fluorine and oxygen on the axis of the center shift significantly along the direction from the O^2? ion to the Yb³⁺ ion during the formation of the tetragonal oxygen center. As this takes place, the distances of both (fluorine and oxygen) ions from the impurity ion increase. The four F^? ions of the nearest octahedral neighborhood of Yb³⁺ that are arranged symmetrically in the plane perpendicular to the axis of the center slightly recede from the axis.     

Low-energy scattering of muonic hydrogen on hydrogen molecules: a semi-classical approach

We present results of PAC measurements in heavy-fermion compound Yb₄As₃. The quadrupole hyperfine interaction has been investigated over the temperature range 78–850 K. The interpretation of the experimental data yields a microscopic proof of the existence of a charge-ordered state with periodic arrangement of Yb²⁺ and Yb³⁺ ions in the low temperature phase. In the high temperature phase all Yb ions are in a valence fluctuating state.     

Energy transfer and fluorescence characteristics of erbium-doped ytterbium aluminum garnet

We have examined the fluorescence characteristics of the garnet-type crystal Yb₃Al₅O₁₂ : Er³⁺ (YbAlG : Er³⁺) and studied the energy transfer process between the two rare earth ions over a temperature range 78–297 K. Certain data were compared with those of YAlG : Er³⁺. In YbAlG : Er³⁺, Yb fluorescence is observed at ?1.03 μm (corresponding to the ²F_5/2 → ²F_7/2 transition); Er fluorescence occurs at ?8500 Å (⁴S_3/2 → ⁴I_13/2 transition) and ?1.6 μm (⁴I_13/2 → ⁴I_15/2 transition). In YAlG : Er³⁺, the same Er lines are observed with the addition of a band at ?1 μ (⁴I_11/2→⁴I_15/2 transition). In YbAlG : Er³⁺, the decay pattern of the Yb emission is purely exponential at all the temperatures examined; the fluorescence lifetime ranges from 36 μ s (at 78 K) to 74 μs(at 269 K). The lifetime of the Er⁴I_13/2 level in the same sample increases from 5.4 ms (at 78 K) to 6.85 ms (at 294 K). The lifetime of this Er level in YAlG : Er³⁺ is weakly temperature dependent over the same range with a value of ?12 ms. Excitation spectra were obtained for the Er 1.53 μm fluorescence in YbAlG : Er³⁺ in order to verify the presence of Yb → Er energy transfer in this sample. The presence of the Yb absorption band (?1 μm) in these spectra provides direct evidence of this energy transfer. The relative enhancement of this Yb band with respect to the Er bands in going from 78 K to 175 K is an indication of a more efficient transfer at the higher temperature. Excitation spectra obtained for the Yb 1.03 μm fluorescence in YbAlG : Er³⁺ revealed the presence of Er → Yb energy transfer as well in this sample. The existence of both Yb → Er and Er → Yb transfer is expected, due to the resonance between the ⁴I_11/2 → ⁴I_15/2 transition of Er and the ²F_5/2 → ²F_7/2 transition of Yb. The above results are explained in terms of a rate equation model in which transfer in both directions is treated in the following manner: Yb → Er transfer is considered to be much more probable than decay processes originating at the Yb ²F_5/2 level; Er → Yb transfer is treated as much more probable than decay processes originating at the Er ⁴I_11/2 level.     

Growth, polarized spectral properties, and 1.5–1.6 μm laser operation of Er:Yb:Sr3Gd2(BO3)4 crystal

An Er:Yb:Sr₃Gd₂(BO₃)₄ crystal was grown by the Czochralski method. The polarized spectral properties of the crystal were investigated, including the polarized absorption and fluorescence spectra and fluorescence decay. The fluorescence quantum efficiency of the upper laser level ⁴I_13/2 of Er³⁺ ions and the efficiency of the energy transfer from Yb³⁺ to Er³⁺ ions were calculated. End-pumped by a diode laser at 970 nm in a hemispherical cavity, a 1.6 W quasi-cw laser at 1.5–1.6 μm with a slope efficiency of 18% and an absorbed pump threshold of 5.9 W was achieved in a 1.8-mm-thick Z-cut Er:Yb:Sr₃Gd₂(BO₃)₄ crystal. This crystal has a flat and broad gain curve at 1.5–1.6 μm and so is also a potential gain medium for tunable and short pulse lasers.     

Additive colouring of CaF2:Yb crystals: determination of Yb2+ concentration in CaF2:Yb crystals and ceramics

When growing CaF₂ crystal doped with rare-earth ions, most of these ions are present in a trivalent state. However, due to contact with graphite crucible, a small proportion of a number of ions (Eu, Sm, Yb and Tm) are reduced to a bivalent state. A similar situation takes place during fabrication of CaF₂ ceramics doped with rare-earth metals. This fact is of particular importance for laser CaF₂:Yb crystals (ceramics), a promising material for short-pulse, high-power, high-energy diode-pumped solid state lasers since the presence of bivalent Yb ions can be a source of thermal losses. To date, there has been no technique to determine Yb²⁺ concentration in as-grown crystals. The proposed technique is based on a total reduction of Yb³⁺ ions via the heating of as-grown CaF₂ crystals with known concentration of Yb in the reducing atmosphere of metal vapour and determining the cross section of absorption bands of Yb²⁺ ions. The knowledge of these parameters allows estimation of the Yb²⁺ content in CaF₂:Yb crystals or ceramics by analysing their absorption spectra. Examples of using this technique are given. The technology of CdF₂ crystals reduction (an “additive colouring”) and features of colouring of crystals doped with rare-earth ions are considered.     

Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Crystal growth, spectral and laser properties of Yb3+:NaGd(WO4)2 crystal

Yb³⁺-doped NaGd(WO₄)₂ (Yb:NGW) crystal has been successfully grown by Czochralski method. The rocking curves from (400) plane of as-grown Yb:NGW crystal was measured and the full-width values at half-maximum was 21″. The polarized absorption spectra, the fluorescence spectra and the fluorescence decay lifetime of Yb:NGW crystal were measured at room temperature. The spectroscopic parameters of Yb:NGW crystal are calculated and compared, with those of Yb:YAG crystal. A continuous wave output power of 3.01 W at 1048 nm was obtained with a slope efficiency of 71% by use of diode pumping.     

A new Yb-doped oxyorthosilicate laser crystal: Yb:Gd2SiO5

A new Yb-doped oxyorthosilicate laser crystal, Yb:Gd₂SiO₅ (Yb:GSO), has been grown by the Czochralski (Cz) method. The crystal structure was determined by means of X-ray diffraction analysis. Room temperature absorption and fluorescence spectra of Yb³⁺ ions in GSO crystal were measured. Then, spectroscopic parameters of Yb:GSO were calculated and compared with those of another Yb-doped oxyorthosilicate crystal Yb:YSO. Results indicated that Yb:GSO crystal seemed to be a very promising laser gain media in generating ultra-pulses and tunable solid state laser applications. As expected, the output power of 2.72 W at 1089 nm was achieved in Yb:GSO crystal with absorbed power of only 4.22 W at 976 nm, corresponding to the slope efficiency of 71.2% through the preliminary laser experiment.     

Spin-spin interaction of Dy3+ ions in KY(WO4)2

The spin-spin interaction of Dy³⁺ ions in a KY(WO₄)₂ single crystal is investigated by electron paramagnetic resonance (EPR) spectroscopy at a temperature of 4.2 K and a frequency of 9.2 GHz. The EPR spectra of ion pairs located in different coordination shells are analyzed. It is revealed that the considerable contribution to the spin-spin interaction of the nearest neighbor ion pair nn is made not only by the magnetic dipole-dipole interaction but also by the isotropic exchange interaction with the parameter I _nn = (+601 ± 17) × 10^?4cm^?1. The exchange interaction in pairs of more widely spaced ions is substantially weaker: I _5n = (?38 ± 3) × 10^?4cm^?1 and I _9n = (+18 ± 4) × 10^?4cm^?1. For the other ion pairs, the magnetic dipole-dipole interaction dominates. It is found that the EPR spectra of single ions and ion pairs exhibit a superhyperfine structure associated with tungsten nuclei.     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Correlation between the negative magnetoresistance effect and magnon excitations in single-crystalline CuCr1.6V0.4Se4

Structural, electrical and magnetic measurements, as well as electron spin resonance (ESR) spectra, were used to characterise the single-crystalline CuCr_1.6V_0.4Se₄ spinel and study the correlation between the negative magnetoresistance effect and magnon excitations. We established the ferromagnetic order below the Curie temperature T _C ≈ 193 K, a p-type semiconducting behaviour, the ESR change from paramagnetic to ferromagnetic resonance at T _C, a large ESR linewidth value and its temperature dependence in the paramagnetic region. Electrical studies revealed negative magnetoresistance, which can be enhanced with increasing magnetic field and decreasing temperature, while a detailed thermopower analysis showed magnon excitations at low temperatures. Spin–phonon coupling is explained within the framework of a complex model of paramagnetic relaxation processes as a several-stage relaxation process in which the V³⁺ ions, the exchange subsystem and conduction electron subsystem act as the intermediate reservoirs.     

EPR and optical spectroscopy of Yb<Superscript>3+</Superscript> ions in CaF<Subscript>2</Subscript>: an analysis of the structure of tetragonal centers

CaF₂ crystals doped with Yb³⁺ ions have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy. EPR spectra of paramagnetic centers (PCs) for cubic (T_c) and tetragonal (T_tet) symmetries were identified. Empirical energy level diagrams were established and crystal field parameters were determined. Information on the CaF₂∶Yb³⁺ phonon spectra was obtained from the electron-vibrational structure of the optical spectra. The crystal field parameters were used to analyze the crystal lattice distortions in the vicinity of the Yb³⁺ ion. Within the framework of a superposition model, it is established that four F⁻ ions located symmetrically with respect to the fourfold axis from the side of the ion-compensator approach the impurity ion and deviate from the PC axis. The second set of four fluorine ions also approaches the Yb³⁺ ion and the PC axis. The ion-compensator F⁻ also approaches considerably the impurity ion.